Process for preparing olefin polymers

Details Process for preparing olefin polymers Process for preparing olefin polymers

2001-03-05

2003-12-09

Harlan, Robert D. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S134000, C526S154000, C526S160000, C526S161000, C526S943000, C502S118000, C502S152000, C502S155000

Reexamination Certificate

active

06660816

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a method for producing an olefin polymer. More particularly, the present invention relates to a method for producing an olefin polymer using a transition metal compound represented by a metallocene complex, which does not require use of an aromatic hydrocarbon as a solvent.
In the present invention, the olefin polymer includes a homopolymer of an olefin and a copolymer of a plurality of olefins.
BACKGROUND ART
It has been reported that a catalyst for polymerization, comprising a transition metal compound, particularly a diimine complex or a transition metal complex containing one or two groups having a cyclopentadiene type anionic skeleton, e.g. a so-called non-metallocene complex or metallocene complex, respectively, and aluminoxane exhibits a high activity. Particularly, when the metallocene complex is used, an olefin polymer having narrow molecular weight distribution and composition distribution, that is, the resulting olefin polymer exhibits considerably useful feature from industrial point of view. Therefore, a lot of reports have recently been made (e.g. Japanese Patent Publication (Kokai) No. Sho 58-19309). It has also been reported that high activity is exhibited in the olefin polymerization in case of a system using no aluminoxane, that is, in a method using a specific boron compound (e.g. Japanese Patent Publication (Kohyo) No. Hei 1-502036, Japanese Patent Publication (Kokai) Nos. Hei 6-157651, Hei3-163088 and Hei3-188092).
Since already known transition metal compounds such as ethylenebis(indenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilyl(tert-butylamide)(tetramethylcyclopentadienyl)titanium dichloride, etc. are soluble in an aromatic hydrocarbon solvent such as toluene, etc., but hardly dissolve in an aliphatic hydrocarbon solvent. Therefore, the transition metal compound was normally handled in the form of a solution of the aromatic hydrocarbon solvent.
Furthermore, the above boron compound is a particulate solid and has a problem that it dissolves in the aromatic hydrocarbon solvent such as toluene, etc. to some extent but its solubility in the other solvent, particularly aliphatic hydrocarbon solvent, is very low. In general, in the polymerization of an olefin using a conventional transition metal compound, it is obliged to use the aromatic hydrocarbon solvent such as toluene, etc. Such a solvent is liable to remain in a polymer as the product to give off an odor, resulting in a large problem.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide a method of producing an olefin polymer using a transition metal compound, which does not require use of an aromatic hydrocarbon solvent which is liable to remain in a polymer as the product to give off an odor.
That is, according to the present invention, there is provided a catalyst for olefin polymerization obtained using (A) and (C) described below or a method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing olefins in the presence of a catalyst for olefin polymerization obtainable by using the following (A) (B) and (C) as catalyst components:
(A): a transition metal complex dissolved, suspended or slurried in an aliphatic hydrocarbon compound;
(B): a compound dissolved, suspended or slurried in an aliphatic hydrocarbon compound, which is selected from the following (B1) to (B3):
(B1) an organoaluminum compound represented by the general formula E
1
a
AlZ
3-a
;
(B2) a cyclic aluminoxane having a structure represented by the general formula {—Al(E
2
)—O—}
b
; and
(B3) a linear aluminoxane having a structure represented by the general formula E
3
{—Al(E
3
)—O—}
c
AlE
3
2
(wherein E
1
to E
3
respectively represents a hydrocarbon group having 1 to 8 carbon atoms, and all of E
1
, E
2
and E
3
may be the same or different; Z represents a hydrogen atom or a halogen atom, and all of Z may be the same or different; a represents a numeral satisfying 0<a≦3; b represents an integer of not less than 2; and c represents an integer of not less than 1); and
(C): at least one boron compound suspended or slurried in an aliphatic hydrocarbon compound, which is selected from the following (C1) to (C3):
(C1) a boron compound represented by the general formula BQ
1
Q
2
Q
3
;
(C2) a boron compound represented by the general formula G
+
(BQ
1
Q
2
Q
3
Q
4
)
−
; and
(C3) a boron compound represented by the general formula (L-H)
+
(BQ
1
Q
2
Q
3
Q
4
)
−
(in each of the above general formulae, B is a boron atom in the trivalent valence state, Q
1
-Q
4
are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a di-substituted amino group, which may be the same or different, respectively. G
+
is an inorganic or organic cation, L is a neutral Lewis base, and (L-H)
+
is a Brønsted acid.)
The present invention will be described in detail hereinafter.
All of the components (A) and component (C) or the additional component (B), which constitute the catalyst for olefin polymerization of the present invention, do not require an aromatic hydrocarbon compound as a solvent. As the solvent for dissolving, suspending or slurrying these catalyst components, an aliphatic hydrocarbon solvent is used.
(A) Transition Metal Component
The component (A) of the catalyst for polymerizing an olefin used in the present invention is a dissolved, suspended or slurried transition metal component.
The transition metal compound is preferably a compound of Group III-XII or lanthanide series of the Periodic Table of the Elements (1993, IUPAC), and various transition metal compounds having an olefin polymerization activity (e.g. metallocene complex, non-metallocene complex, etc.) can be employed. A transition metal compound of Group IV or lanthanide series is more preferred, and a transition metal compound having at least one cyclopentadiene type anionic skeleton, i.e. metallocene transition metal compound is most preferred.
The metallocene transition metal compound is a compound represented by the following general formula (3): General formula (3) ML
a
R
3
p-a
(wherein M represents a transition metal compound of Group IV or lanthanide series of the Periodic Table of the Elements (1993, IUPAC); L represents a group having a cyclopentadiene type anionic skeleton or a group having a hetero atom, at least one of which is a group having a cyclopentadiene type anionic skeleton, and a plurality of L may be the same or different and may be crosslinked each other; R
3
represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms; a represents a numeral satisfying 0<a≦p; and p represents a valence of a transition metal atom M).
In the general formula (3) representing the metallocene transition metal compound, M is a transition metal compound of Group IV or lanthanide series of the Periodic Table of the Elements (1993, IUPAC). Specific examples of the transition metal atom of Group IV include a titanium atom, a zirconium atom, a hafnium atom, etc., and specific examples of the transition metal atom of lanthanide series include a samarium atom. Among them, titanium atom, zirconium atom or hafnium atom is preferred.
In the general formula (3) representing the metallocene transition metal compound, L is a group having a cyclopentadiene type anionic skeleton or a group having a hetero atom, at least one of which is a group having a cyclopentadiene type anionic skeleton, and a plurality of L may be the same or different and may be crosslinked each other.
Examples of the group having a cyclopentadiene type anionic skeleton include &eegr;
5
-cyclopentadienyl group, &eegr;
5
-substituted cyclopentadienyl group or a polycyclic group having a cyclopentadiene type anionic skeleton. Examples of the substituent of the &eegr;
5
-substituted cyclopentadienyl group include hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms or silyl group

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